Process for breaking petroleum emulsions



Patented Feb. 20, 1951 UNITED STATES PATENT OFFICE PROCESSES FORBREAKING PETROLEUM EMULSION S No Drawing. Application May 6, 1949,Serial No. 91,884

9 Claims. (Cl. 252--345) This invention relates to processes orprocedures particularly adapted for preventing, breaking, or resolvingemulsions of the waterin-oil type, and particularly petroleum emulsions.We have found that if certain hydrophile hydroxylated synthetic productsare treated with one or more moles of epichlorohydrin the resultantproduct is particularly effective as a demulsifier, and also has otherutilities in other arts, as, for example, serving as an intermediate forthe manufacture of more complex organic compounds.

In the process of demulsification We are inclined to suspect that thereis a slight amount of hydrolysis at the interface after the demulsifying agent has been absorbed, and, thus, hydrochloric acid is generatedin minute amounts which appear to effect the stability of the emulsion,or, stated conversely, increases the effectiveness of the demulsifier.

The hydrophile hydroxylated synthetic products employed as initialmaterials for reaction with epichlorhydrin, have been described in anumber of our co-pending applications, for example, Serial No. 8,722(now Patent No. 2,499,365), Serial No. 8,723 (now Patent No. 2,499,366),and Serial No. 8,730 (now abandoned), all filed February 16, 1948, andSerial No. 42,133, filed August 2, 1948 (now abandoned). See also ourco-pending applications, Serial Nos. 64,468 (now abandoned), and 64,469,both filed December 8, 1948.

Complementary to the above aspect of our invention is our companioninvention concerned with the new chemical products or compounds .used asthe demulsiiying agents in said aforementioned processes or procedures,as Well as the application of such chemical compounds, products, and thelike in various other arts and industries, along with the method formanufacturing said new chemical products or compounds which are ofoutstanding value in demulsification. See our co-pending applicationSerial No. 91,885, filed May 6, 1949-.

Our invention provides an economical and rapid process for resolvingpetroleum emulsions of the water.in-oi1 type that are commonly referredto as cut oil, roily oil, emulsified oil, etc., and which comprise finedroplets of naturally-occurring waters or brines dispersed in a more orless permanent state throughout the oil which constitutes the continuousphase of the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crude oil and relatively soft waters or weakbrines. Controlled emulsification and subsequent demulsification underthe conditions just mentioned are of significant value in removingimpurities, particularly inorganic salts, from pipeline oil.

Demulsification, as contemplated in the present application, includesthe preventive step of commingling the demulsifier with the aqueouscomponent which would or might subsequently become either phase of theemulsion in the absence of such precautionary measure. Similarly, suchdemulsifier may be mixed with the hydrocarbon component.

Thus, the present invention is concerned with breaking petroleumemulsions of the water-inoil type, characterized by subjecting theemulsion to the action of a chloro-oxypropylated derivative ofhydrophile hydroxylated synthetic products; said hydrophile syntheticproducts being oxyalkylation products of (A) An alpha-beta alkyleneoxide having not more than 4 carbon atoms and selected from the classconsisting of ethylene oxide, propylene oxide, butylene oxide, glycide,and methylglycide; and

(B) An oxyallgvlation-susceptible, fusible, organic solvent-soluble,water-insoluble, phenol aldehyde resin; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and 1 V 3 substituted in the 2,4,6 position; saidoxyalkylated resin being characterized by the introduction into theresin molecule of a plurality of divalent radicals having the formula(R)n, in which R1 is a member selected from the class consisting ofethylene radicals, propylene radicals, butylene radicals,hydroxypropylene radicals, and'hydroxybutylene radicals, and n is anumeral varying from 1 to with the proviso that at least 2 moles of.alkylene oxide be introduced for each phenolic nucleus; saidchlorooxypropylated compounds being obtained by reaction Withepichlorohydrin; and with the final proviso that the hydrophileproperties of the chloro-oxypropylated derivative as well as theoxyalkylated resin in an equal weight of xylene are sufiicient toproduce an emulsion when said xylene solution is shaken vigorously withone to three volumes of water.

For purpose of convenience, what is said hereinafter will be dividedinto four parts. Part 1 will be concerned with the production of theresin from a difunctional phenol and an aldehyde; Part 2 will beconcerned with the oxyalkylation of the resin so as to convert it into ahydrophile hydroxylated derivative; Part 3 will be concerned with theconversion of the immediately aforementioned compound, or the like, intoachloro-oxypropylated derivative by means of epichlorohydrin; and Part 4will be concerned with the use of such derivatives, obtained by means ofepichlorohydrin, as demulsifiers, as hereinafter described.

PART 1 As to the preparation of the phenol-aldehyde resins, reference ismade to our co-pending applications Serial Nos. 8,730 and 8,731, bothfiled February 16, 1948 (both now abandoned). In such co-pendingapplications we described a fusible, organic solvent-soluble,water-insoluble resin polymer of the formula:

R n R In such idealized representation 12" is a numeral Varying from 1to 13, or even more, provided that the resin is fusible and organicsolvent-soluble. R is a hydrocarbon radical having at least 4 and notover 8 carbon atoms. In the instant application R may have as many as 12carbon atoms, as in the case of a resin obtained from a dodecylphenol.In the instant invention it may be first suitable to describe thealkylene oxides employed as reactants, then the aldehydes, and finally,the phenols, for the reason that the latter require a more elaboratedescription.

The alkylene oxides which may be used are the alpha-beta oxides havingnot more than 4 carbon atoms, to wit, ethylene oxide, alpha-betapropylene oxide, alpha-beta butylene oxide, glycide, and methylglycide.T

Any aldehyde capable offorming a methylol or a substituted methylolgroup and having not more than 8 carbon atoms is satisfactory, so longcation reaction, or with the subsequent oxyalkylation of the resin, butthe use of formaldehyde, in its cheapest form of an aqueous solution,for the production of the resins is particularly advantageous. Solidpolymersof formaldehyde are more expensive and higher aldehydes are bothless reactive, and are more expensive. Furthermore, the higher aldehydesmay undergo other reactions which are not desirable, thus introducingdifficulties into the resinification step. Thus, acetaldehyde, forexample, may undergo an aldol condensation, and it and most of thehigher aldehydes enter into self-resinification when treated with strongacids or alkalies. On the other hand, higher aldehydes frequentlybeneficially aifect the solubility and fusibility of a resin. This isillustrated. for example, by the different characteristics of the resinprepared from para-tertiary amylphenol and formaldehyde on one hand, anda comparable product prepared from the same phenolic reactant andheptaldehyde on the other hand. The former,

as shown in certain subsequent examples, is a hard, brittle, solid,whereas, the latter is soft and tacky, and obviously easier to handle inthe subsequent oxyalkylation procedure. p 7

Cyclic aldehydes may be employed, particularly Ibenzaldehy'de. Theemployment of furfural requires careful control, for the reason that inaddition to its aldehydic function, furfural can form vinylcondensations by virtue of its unsaturated structure. The production ofresins from furfural for use in preparing reactants for the presentprocess is most conveniently conducted with weak alkaline catalysts andoften with alkali metal carbonates. Useful aldehydes, in addition toformaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde,2-ethylhexanal, ethylbutyraldehyde, heptaldehyde, and. benzaldehyde,furfural and glyoxal. It would appear that the use of glyoxal should beavoided, due to the fact that it is tetrafunctional. However, ourexperience has been that, in resin manufacture and particularly asdescribed herein, apparently only one of the aldehydic functions entersinto the resinification reaction. The inability of the other aldehydicfunction to enter into the reaction is presumably due to sterichindrance. Needless to say, one can use a mixture of two or morealdehydes, although usually this has no advantage.

Resins of the kindwhich are used as intermediates in this invention areobtained with the use of acid catalysts or alkaline catalysts, or

. without the use of any catalyst at all. Among the useful alkalinecatalysts are ammonia, amines, and quaternary ammonium bases. It isgenerally accepted that when ammonia and amines are employed ascatalysts, they enter into the condensation reaction, and in fact, mayoperate by initial combination with the aldehydic reactant. mineillustrates such a combination. In'light of these various reactions, itbecomes difiicult to present any formula which would depict thestructure of the various resins prior to oxyalkylation. More will besaid subsequently as to the difierence between the use of an alkalinecatalyst and an acid catalyst; even in theme of an alkaline catalyst,there is considerable evidence to indicate that the products are notidentical where different basic materials are employed. The basicmaterials employed include not only those previously enumerated, butalso the hydroxides of the alkali metals, hydroxides of the The compoundhexamethylenetetra-' alkaline earth metals, salts'of strong bases andweak acids, such as sodium acetate, etc.

Suitable phenolic reactants include the following:Para-tertiary-butylphenol; para-secondarybutylphenol;para-tertiaryamylphenol; para-secondary-amylphenol;para-tertiaryhexylphenol; para-isooctylphenol; ortho-phenylphenol;paraphenylphenol; ortho-benzylphenol; para-benzylphenol; andparacyclohexylphenol, and the corresponding ortho-para-substitutedinetacresols and 3,5-xylenols. Similarly, one may use paraorortho-non-ylphenol or a mixture, paraor ortho-decylphenol or a mixture,menthylphenol, or para or ortho-dodecylphenol. For convenience, thephenol has previously 'been referred 'to' as monocyclic, in order todifferentiate from fused nucleus polycyclic phenols, such as substitutednaphthols. Specifically, monocyclic is limited to the nucleus in whichthe hydroxyl radical is attached. Broadly speaking, where a substituentis cyclic, particularly aryl, obviously in the usual sense such phenolis actually polycyclic, although the phenolic hydroxyl is not attachedto a fused polycyclic nucleus. Stated another way, phenols in which thehydroxyl group is directly attached to a condensed or fused polycyclicstructure, are excluded. This matter, however, is clarified by thefollowing consideration. The phenols heren contemplated for reaction maybe indicated by the following formula:

in which R is selected from the class consisting of hydrogen atoms andhydrocarbon radicals having at least 4 carbon atoms and not more than 12carbon atoms, with the proviso that one occurrence of R is thehydrocarbon substituent and the other two occurrences are hydrogenatoms, and with the further provision that one or both of the 3 and 5positions may be methyl substituted.

The above formula possibly can be restated more conveniently in thefollowing manner, to wit, that the phenol employed is of the followingformula, with the proviso that R is a hydrocarbon substituent located inthe 2,4,6 position, again with the provision as to 3 or 3,5 methylsubstitution. This is conventional nomenclature, numbering the variouspositions in the usual clockwise manner, beginning with the hydroxylposition as one:

The manufacture of thermoplastic phenolaldehyde resins, particularlyfrom formaldehyde and a difunctional phenol, i. e., a phenol inwhichfione; of the three reactivepositions (2,4,6)- has been substitutedby a hydrocarbon group, and particularly by one having at least 4 carbonatoms and not more than 12 carbon atoms, is Well known. As has beenpreviously pointed out, there is no objection to a methyl radicalprovided it is present in the 3 or 5 position.

Thermoplastic or fusible phenol-aldehyde resins are usually manufacturedfor the varnish trade and oil solubility is of prime importance. Forthis reason, the common reactants employed are butylated phenols,amylated phenols, phenylphenols, etc. The methods employed inmanufacturing such resins are similar to those employed in themanufacture of ordinary phenol-formaldehyde resins, in that either anacid or alkaline catalyst is usually employed. The procedure usuallydiffers from that employed in the manufacture of ordinary phenolaldehyderesins in that phenol, being watersoluble, reacts readily with anaqueous aldehyde solution without further difficulty, While when awater-insoluble phenol is employed some modification is usually adoptedto increase the interfacial surface and thus cause reaction to takeplace. A common solvent is sometimes employed. Another procedure employsrather severe agitation to create a large interfacial area. Once thereaction starts to a moderate degree, it is possible that both reactantsare somewhat soluble in the partially reacted mass and assist inhastening the reaction. We have found it desirable to employ a smallproportion of an organic sulfo-acid as a catalyst, either alone or alongwith a mineral acid like sulfuric or hydrochloric acid. For example,alkylated aromatic sulfonic acids are effectively employed. Sincecommercial forms of such acids are commonly their alkali salts, it issometimes convenient to use a small quantity of such alkali salt plus asmall quantity of strong mineral acid, as shown in the examples below.If desired, such organic sulfo-acids may be prepared in situ in thephenol employed, by reacting concentrated sulfuric acid with a smallproportion of the phenol. In such cases where xylene is used as asolvent and concentrated sulfuric acid is employed, some sulfonation ofthe xylene probably occurs to produce the sulfo-acid. Addition of asolvent such as xylene is advantageous as hereinafter described indetail. Another variation of procedure is to employ such organicsulfo-acids, in the form of their salts, in connection with analkali-catalyzed resinification procedure. Detailed examples areincluded subsequently.

Another advantage in the manufacture of the thermoplastic or fusibletype of resin by the acid catalytic procedure is that, since adifunctional phenol is employed, an excess of an aldehyde,

for instance formaldehyde, may be employed without too marked a changein conditions of reaction and ultimate product. There is usually little,if any, advantage, however, in using an excess over and above thestoichiometric proportions for the reason that such excess may be lostand wasted. For all practical purposes the molar ratio of formaldehydeto phenol may be limited to 0.9 to 1.2, with 1.05 as the preferredratio, or sufficient, at least theoretically, to convert the remainingreactive hydrogen atom of each terminal phenolic nucleus. Sometimes whenhigher aldehydes are used an excess of aldehydic reactant can bedistilled off and thus recovered from the reaction mass. This sameexample, per mole 'of phenol, or even more, with the result that only asmall part of such aldehyde remains uncombined or is subsequentlyliberated during resinification. Structures which have been advanced toexplain such increased use of aldehydes are the following:

Such structures may lead to the production of cyclic polymers instead oflinear polymers. For this reason, it has been previously pointed outthat, although linear polymers have by far the most importantsignificance, the present invention does not exclude resins of suchcyclic structures.

Sometimes conventional r'esinification procedure is employed usingeither acid or alkaline catalysts to produce low-stage resins. Suchresins may be employed as such, or may be altered or converted intohigh-stage resins, or in any event, into resins of higher molecularweight, by heating along with the employment of vacuum so as to splitoff water or formaldehyde, or both. Generally speaking, temperaturesemployed, particularly with vacuum, may be in the neighborhood of 175 to250 C., or thereabouts.

It may be well to point out, however, that the amount of formaldehydeused may and does usually affect the length of the resin chain. Ill--creasing the amount of the aldehyde, such as formaldehyde, usuallyincreases the size or molecular weight of the polymer.

In the hereto appended claims there is specified, among'other things,the resin polymer containing at least 3 phenolic nuclei. Such mini mummolecular size is most conveniently determin-ed as a rule by cryoscopicmethod using benzene, or some other suitable solvent, for instance, oneof those mentioned elsewhere herein as -a solvent for such resins. As amatter of fact, using the procedures herein described or anyconventional resinification procedure will yield products usually havingdefinitely in excess of 3. nuclei. In other words, a resin having anaverage of 4, 5 or 5% nuclei per unit is apt to be, formed as a minimumin resinification, except, under certain special conditions wheredimerization may occur; However, if resins are prepared at substantiallyhigher temperatures, substituting cymene, tetra-, lin, etc., or someother suitable solvent which boils or'reiiuxes at a higher temperature,instead of xylene, in subsequent examples, and if one doubles or triplestheamount of catalyst; doubles or triples the time of refluxing, uses amarked excess of formaldehyde or other aldehyde, then the average sizeof the resin is apt to be distinctly over the above values, for example,it may average 7 to 15 units. Sometimes the expression lowstage resin orlow-stage intermediate is emi ployed to mean a stage having 6 or '7units or even less. In the appended claims we have used low-stage? tomean 3 to '7 units based on average molecular weight.

The molecular weight determinations, of course, require that the productbe completely soluble in the particular solvent selected as, forinstance, benzene. The molecular weight determination of such solutionmay involve either the freezing point as in the cryoscopic method, or,

' less conveniently perhaps, the boiling point in an ebullioscopicmethod. The advantage of the ebullioscopic method is that, in comparisonwith the cryoscopic method, it is more apt to insure completesolubility. One such common method to employ is that of Menzies andWright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitablemethod for determining molecular weights will serve, although almost anyprocedure adopted hasinherent limitations. A good method for determiningthe molecular weights of resins, especially solvent-soluble resins, isthe cryoscopic procedure of Krumbhaar which employs diphenylamine as asolvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co.1947).

Subsequent examples will illustrate the use of an acid catalyst, analkaline catalyst, and no catalyst. As far as resin manufacture per seis concerned, we prefer to'use an acid catalyst, and particularly amixture of an organic sulfo-acid and a mineral acid, along with asuitable solvent, such as xylene, as hereinafter illustrated in detail.;I-Iowever, we have obtained products from resins obtained by use of analkaline catalyst which were just as satisfactory as those obtainedemploying acid catalysts. Sometimes a combination of both types ofcatalysts is used in different stages of resinification. Resins soobtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., thosereferred to as high-stage resins, are conveniently obtained bysubjecting lower molecular weight resins to vacuum distillation andheating. Although such procedure sometimes removes only a modest amountor even perhaps no low polymer, yet it is almost certain to producefurther polymerization. For instance, acid catalyzed resins obtained inthe usual manner and having a molecular weight indicating the presenceof approximately phenolic units or thereabouts may be subjected to suchtreatment, with the result that one obtains a resin having approximatelydouble this molecular weight. The usual procedure is to use a secondarystep, heating the resin in the presence or absence of an inert gas,including steam, or by use of vacuum.

We have found that under the usual conditions of resinificationemploying phenols of the kind here described, there is little or notendency to form binuclear compounds, i. e., dimers, resulting from thecombination, for example, of 2 moles of a phenol and one mole offormaldehyde, particularly where the substituent has 4 or 5 carbonatoms. Where the number of carbon atoms in a substituent approximatesthe upper limit specified herein, there may be some tendency todimerization. The usual procedure to obtain a dimer involves anenormously'large excess of the phenol, for instance, 8 to 10 moles permole of aldehyde. Substituted dihydroxydiphenylmethanes obtained fromsubstituted phenols are not resins as that term is used herein.

A'though any conventional procedure ordinarily employed may be used inthe manufacture of the herein contemplated resins or, for that matter,such resins may be purchased in the open market, we have found itparticularly desirable to use the procedures described elsewhere herein.and employing a combination of an organic sulfoacid and a mineral acidas a catalyst, and xylene as a solvent. Byway of illustration, certainsub- V sequent examples are included, but it is to be understood theherein described invention is not concerned with the resins per se orwith any particular method of manufacture but is concerned with the useof reactants obtained by the subsequent oxyalkylation thereof. Thephenolaldehyde resins may be prepared in any suitable manner.

Oxyalkylation, particularly oxyethylation which is the preferredreaction, depends on contact between a non-gaseous phase and a gaseousphase. It can, for example, be carried out by melting the thermoplasticresin and subjecting it to treatment with ethylene oxide or the like, orby treating a suitable solution or suspension. Since the melting pointsof the resin are often higher than desired in the initial stage ofoxyethylation, we have found it advantageous to use a solution orsuspension of thermop astic resin in an inert solinert towards thereactants and also-inert towards water. Numerous solvents, particularlyof aromatic or cyclic nature, are suitably adapted for such use.Examples of such solvents are xylene, cymene, ethyl benzene, propylbenzene, mesitylene, decalin (tetrahydronaphthalene) ethylene glycoldiethylether, diethylene glycol diethylether, and tetraethylene glycoldimethylether, or mixtures of one or more. Solvents such asdichloroethylether, or

dichlo-ropropylether may be employed either alone i or in mixture buthave the objection that the chlorine atom in the compound may slowlycombine with the alkaline catalyst employed in oxyethylation. Suitablesolvents may be selected from this group for molecular weightdeterminations.

The use of such solvents is a convenient expedient in the manufacture ofthe thermoplastic resins, particularly since the solvent gives a moreliquid reaction mass and thus prevents overheating, and also because thesolvent can be employed in connection with a reflux condenser and awater trap to assist in the removal of water of reaction and also waterpresent as part of the formaldehyde reactant when an aqueous solution offormaldehyde is used. Such aqueous solution, of course, with theordinary product of commerce containing about 3'7 to 40% formaldehyde,is the preferred reactant. When such solvent is used it isadvantageously added at the beginning (decahydronaphthalene) tetralin ofthe resinification procedure or before the reaction has proceeded veryfar.

The solvent can be removed afterwards by distillation with or withoutthe use of vacuum, and a final higher temperature can be employed tcomplete reaction if desired. In many instances it is most desirable topermit part of the solvent, particularly when it is inexpensive, e. g.,xylene, to remain behind in a predetermined amount so as to have a resinwhich can be handled more conveniently in the oxyalkylation stage. If amore expensive solvent, such as decalin, is employed, xylene or otherinexpensive solvent may be added after the removal of decalin, ifdesired.

In preparing resins from difunctional phenols it'is common to employreactants of technical grade. The substituted phenols hereincontemplated are usually derived from hydroxybenzene. As a rule, suchsubstituted phenols are comparatively free from unsubstituted phenol. Wehave generally found that the amount present is considerably less than1% and not infrequently in the neighborhood of of 1%, or even less. Theamount of the usual trifunct'onal phenol, such as hydrox'ybenzene ormetacresol, which can be tolerated is determined by the fact that actualcross-linking, if it takes place even infrequently, must not besufficient to cause insolubility at the completion of the resinificationstage or the lack of hydrophile properties at the completion of theoxyalkylation stage.

The exclusion of such trifunctional phenols as hydroxybenzene ormetacresol is not based on the fact that the mere random or occasionalinclusion of an unsubstituted phenyl nucleus in the resin molecule or inone of several molecules, for exam ple, markedly alters thecharacteristics of the oxyalkylated derivative. The presence of a phenylradical having a reactive hydrogen atom available or having ahydroxymethylol or a substituted hydroxymethylol group present is apotential source of cross-linking either during resinification oroxyalkylation. Cross-linking leads either to insoluble resins or tonon-hydrophilic products resulting fromthe oxyalkylation procedure. Withthis rationale understood, it is obvious that trifunctional phenols aretolerable only in a minor proportion and should not be present to theextent that insolubility is produced in the resins, or that the productresulting from oxyalkylation is gelatinous rubbery, or at least nothydrophile. As to the rationale of resinification, note particularlywhat is said hereafter in differentiating between resoles, Novolaks, andresins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organicsolvent-soluble resins are usually linear but may be cyclic. Such morecomplicated structure may be formed, particularly if a resin prepared inthe usual manner is converted into a higher stage resin by heattreatment in vacuum as previously mentioned. This again is a reason foravoiding any opportunity for crosslinking due to the presence of anyappreciable amount of trifunctional phenol. In other words, the presenceof such reactant may cause crosslinking in a conventional resinificationprocedure, or in the oxyalkylation procedure, or in the heat and vacuumtreatment if it is employed as part of resin manufacture.

Our routine procedure in examining a phenol for suitability forpreparing intermediates to be used in practicing the invention is toprepare a resin employing formaldehyde in excess (1.2 moles offormaldehyde per mole of phenol) and using an fusible resins.

'1'! acid catalyst in the manner described in Example la Of our Patent2,499,370, granted March 7, 1950. If the resin so obtained issolvent-soluble in any one of the aromatic or other solvents pre viouslyreferred to, it is then subjected to oxyethylation. During oxyethylationa temperature is employed of approximately 150 to 165 C. with additionof at least 2 and advantageously up to 5 moles of ethylene oxide perphenolic hydroxyl. The

oxyethylation is advantageously conducted so as to require from a fewminutes up to 5 to hours. If the product so obtained is solvent-solubleand self -dispersing or emulsifiable, or has emulsifying properties, thephenol is perfectly satisfactory from the standpoint of trifunctionalphenol content. The solvent may be removed prior to the 'dispersibilityor emulsifiability test.

When a product becomes rubbery during oxyalkylation due to the presenceof a small amount of trireactive an anomaly or a contradiction of whatis sometimes said in regard to resinification reactions involvingdifunctional phenols only. This is presumably due to cross-linking. Thisappears to be contradictory to what one might expect in light of thetheory of functionality in resinification. It is true that underordinary circumstances, or rather under the circumstances ofconventional resin manufacture, the procedures employing difunctionalphenols are very apt to, and almost invariably do, yieldsolvent-soluble,

However, when conventional procedures are employed in connection withresins for varnish manufacture or the like, there is involved thematterof color, solubility in oil, etc. When resins of the same type aremanufactured for the herein contemplated purpose, 1. e., as a rawmaterial to be subjected to oxyalkylation, such criteria of selectionare no longer pertinent. Stated another way, one may use more drasticconditions of resinification than those ordinarily employed to produceresins for the present purposes. Such more drastic conditions ofresinification may include increased amounts of catalyst, highertemperatures, longer time of reaction, subsequent reaction involvingheat alone or in combination with vacuum, et-c. Therefore, one is notonly concerned with the resinification reactions which yield the bulk ofordinary resins '12 his co-workers, and others. As to a bibliography ofsuch investigations, see Carswell, Phenoplasts, chapter 2. Theseinvestigators limited much of their work to reactions involving phenolsfrom difunctional phenols but also and particularly with the minorreactions of ordinary resin manufacture which are 'of importance in thepresent inventionfor the reason that they occur under more drasticconditions of resinification which may be employed advantageously attimes,

and they may lead to cross-linking.

In this connection it may be well to point out that part of thesereactions are now understood or .Hultzsch and his associates, and to vonEulen and having two or less reactive hydrogen atoms. Much of whatappears in these most recent and most up-to-date investigations ispertinent to the present invention insofar that much of it is referringto resinification involving difunctional phenols.

For th moment, it may be simpler to consider a most typical type offusible resin and forget for the time that such resin, at least undercertain circumstances, is susceptible to further'complications.Subsequently in the text it will be pointed out that cross-linking orreaction with excess formaldehyde may take place even with one of suchmost typical type resins. This point is made for the reason thatinsolubles must be avoided in order to obtain the products hereincontemplated for use as reactants.

The typical type of fusible resin obtained from a para-blocked orortho-blocked phenol is clearly differentiated from the Novolaktype orresole type of resin. Unlike the resole type, such typical typepara-blocked or ortho-blocked phenol resin may be heated indefinitelywithout passing into an infusible stage, and in this respect is similarto a Novolak. Unlike the Novolak type the addition of a furtherreactant, for instance, more aldehyde, does not ordinarily alterfusibility of the difunctional phenol-aldehyde type resin; but suchaddition to a Novolak causes cross-linking by virtue of the availablethird functional position.

What has been said immediately preceding is subject to modification inthis respect: It is well known, for example, that difunctional phenols,for instance, paratertiaryamylphenol, and an aldehyde, particularlyformaldehyde, may yield heat-hardenable resins, at least under certainconditions, as for example the use of two moles of formaldehyde to oneof phenol, along with an alkaline catalyst. This peculiar hardening orcuring or cross-linking of resins obtained from difunctional phenols hasbeen recognized by various authorities.

The intermediates herein used must be hydrophile or sub-surface-activeor surface-active as hereinafter described, and this recludes theformation of insolubles during resin manufacture or the subsequentstageof resin manufacture where heat alone, or heat and vacuum, areemployed, or in the oxyalkylation procedure. In its simplestpresentation the rationale of resinification involving formaldehyde, forexample, and a difunctional phenol would not be expected to formcrosslinks. However, cross-linking sometimes occurs and it may reach theobjectionable stage. However, provided that the preparation of resinssimply takes into cognizance the present knowledge of the subject, andemploying preliminary, exploratory routine examinations as hereinindicated, there is not the slightest difficulty in preparing a verylarge number of resins of various types and from various reactants, andby means of different catalysts by different procedures, all of whichare eminently suitable for the herein described purpose.

Now returning to the thought that cross-linking can take place, evenwhen difunctional phenols are used exclusively, attention is directed tothe following: Somewhere during the course of resin manufacture theremay be a potential cross-linkin combination formed but actualcross-linking may not take placeuntil the subsequent stage isreached, 1. e., heat and vacuum stage, or oxyalkylation stage. Thissituation may be related or explained in terms of a theory of flaws, orLockerstellen, which is employed in explaining flaw-forming groups dueto the fact that a CI-IzOH radical and H atom may not lie in the sameplane in the manufacture of ordinary phenol-aldehyde resins.

Secondly, the formation or absence of formation of insolubles may berelated to the aldehyde used and the ratio of aldehyde, particularlyformaldehyde, insofar that a slight variation may, under" circumstancesnot understandable, produce insolubilization. The formation of theinsoluble resin is apparently very sensitive to the quantity offormaldehyde employed and a slight increase in the proportion offormaldehyde-may lead to the formation of insoluble gel lumps. The causeof insoluble resin formation is not clear, and nothing is known as tothe structure of these resins.

All that has been said previously herein as regards resinification hasavoided the specific reference to activity of a methylene hydrogen atom.Actually there is a possibility that under some drastic conditionscross-linking may take place through formaldehyde addition to themethylene bridge, or some other reaction involving a methylene hydrogenatom.

Finally, there is some evidence that, although the meta positions arenot ordinarily reactive, possibly at times methylol groups or the likeare formed at the meta positions; and if this were the case it may be asuitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instanceformaldehyde, is not to be taken as a criterion of rejection for use asa reactant. In other words, a phenol-aldehyde resin which isthermoplastic and solvent-soluble, particularly if xylene-soluble, isperfectly satisfactory even though retreatment with more aldehyde may achange its characteristics markedly in regard to both fusibility andsolubility. Stated another way, as far as resins obtained fromdifunctional phenols are concerned, they may be eitherformaldehyde-resistant or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactants, it is tobe noted that they are thermoplastic phenol-aldehyde resins derived fromdifunctoinal phenols and are clearly distinguished from Noyolaks orresoles. When these resins are produced from difunctional phenols andsome of the higher aliphatic aldehydes, such as acetaldehyde, theresultant is often a comparatively soft or pitchlike resin at ordinarytemperature. Such resins become comparatively fluid at 110 to 165 C. asa rule and thus can be readily oxyalkylated, preferably oxyethylated,without the use of a solvent.

Reference has been made tothe use of the word fusible. Ordinarily athermoplastic resin is identified as one which can be heated repeatedlyand still not lose its thermoplasticity. It is recognized, however, thatone may have a resin which is initially thermoplastic but on repeatedheating may become insoluble in an organic solvent, or at least nolonger thermoplastic, due to the fact that certain changes take placevery slowly. As far as thepresent i vention is concerned, it is obviousthat a resin to be suitable need only be sufficiently fusible to permitprocessing to produce our oxyalkylated products and not yield insolublesor cause insolubilization or gel formation, or rubberiness, aspreviously described. Thus resins which are, strictly speaking, fusiblebut not necessarily thermoplastic in the most rigid sense that suchterminology would be appleid to the mechanical properties of a resin,are useful intermediates. The bulk of all fusible resins of the kindherein described are thermoplastic.

The fusible or thermoplastic resins, or solventsoluble resins, hereinemployed as reactants, are water-insoluble, or have no appreciablehydrophile properties. The hydrophile property is introduced byoxyalkylation. In the hereto ap pended claims and elsewhere theexpression water-insoluble is used to point out this char acteristic ofthe resins used.

In the manufacture of compounds herein employed. particularly fordemulsification, it is obvious that the resins can be obtained by one ofa number of procedures. In the first place, suitable resins are marketedby a number of companies and can be purchased in the open market; in thesecond place, there are a wealth of examples of suitable resinsdescribed in the literature. The third procedure is to follow thedirections of the present application.

The polyhydric reactants, i. e., the oxyalkylation-susceptible,water-insoluble, organic solventsoluble, fusible, phenol-aldehyde resinsderived from difunctional phenols, used as intermediates to produce theproducts used in accordance with the invention, are exemplified by Exmples Nos. 1a through 10311 of our Patent 2,499,370, granted March '7,1950, and reference is made to that patent for examples of theoxyalkylated resins used as intermediates.

Previous reference has been made to the use of a single phenol as hereinspecified, or a single reactive aldehyde, or a single oxyalkylatingagent. Obviously, mixtures of reactants may be employed, as for examplea mixture of para-butylphenol and para-ainylphenol, or a mixture ofpara-butylphenol and para-hexylphenol, or parabutylphenol andpara-phenylphenol. It is ex tremely difficult to depict the structure ofa resin derived from a single phenol. When mixtures of phenols are used,even in equimolar proportions, the structure of the resin is even moreindeterminable. In other words, a mixture involving para-butylphenol andpara-amylphenol might have an alternation of the two nuclei or one mighthave a series of butylated nuclei and then a series of amylated nuclei.If a mixture of aldehydes is employed, for instance, acetaldehyde andbutyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde andacetaldehyde, the final structure of the resin becomes even morecomplicated and possibly depends on the relative reactivity of thealdehydes. For that matter, one might be producing simultaneously twodifferent resins, in what would actually be a mechanical mixture,although such mixture might exhibit some unique properties as comparedwith a mixture of the same two resins prepared separately. Similarly, ashas been suggested, one might use a combination of oxyalkylating agents:for instance, one might partially oxyalhylate with ethylene oxide andthen fini h -with propylene oxide. It is understood that theoxyalkylated derivatives of such resins, derived fr such piurality ofreactants. instead of bein mitcd to single reactant from each of thethree classes, is contemplated and here included for the son that theyare obvious variants.

fost

PART 2" Having obtained a suitable resin of the kind described, suchresin is subjected to treatment with a low molal reactive alpha-betaolefine oxide so as to render the product distinctly hydrophile innature, as indicated by the fact that it becomes self-emulsifiable ormiscible or soluble in water, or seli-dispersible, or has emulsifyingproperties. The olefine oxides employed are characterized by the factthat they contain not over 4 carbon atoms and are selected from theclass consisting of ethylene oxide, propylene oxide, butylene oxide,glycide, and methylglycide. Glycide may be, of course, considered as ahydroxypropylene oxide and methyl glycide as a 'hydroxy butylene oxide.In any event, however, all such reactants contain the reactive ethyleneoxide ring and may be best considered as derivatives of or substitutedethylene oxides. The solubilizing efiect of the oxide is directlyproportional to the percentage of oxygen present, or specifically, tothe oxygencarbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is2:3; and in methyl glycide, 1:2. In such compounds, the ratio is veryfavorable to the production of hydrophile or surfaceactive properties.However, the ratio, in propylene oxide, is 1:3, and in butylene oxide,1:4. Obviously, such latter two reactants are satisfactorily employedonly where the resin composition is such as to make incorporation ofthedesired property practical. In other cases, they may producemarginally satisfactory derivatives, or

even unsatisfactory derivatives. They are usable in conjunction wtih thethree more favorable alkylene oxides in all cases. For instance, afterone or several propylene oxide or butylene oxide mol cules have beenattached to the resin molecule, oxyalkylation may be satisfactorilycontinued using the more favorable members of the class, to produce thedesired hydrophile product.

Used alone, these two reagents may-in some cases fail to producesufficiently hydrophile derivatives because of their relatively lowoxygen-carbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, andpropylene oxide is more effective than butylene oxide. Hydroxy propyleneoxide (glycide) is more effective than propylene oxide. Similarly,hydroxy butylene oxide (methyl glycide) is more effective than butyleneoxide. Since ethylene oxide is the cheapest alkylene oxide available andis reactive, its'use is definitely advantageous, and especially in lightof its high oxygen content. Propylene oxide is less reactive thanethylene oxide, and butylene oxide is definitely less reactive thanpropylene oxide. On the other hand, glycide may react' with almostexplosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind from which the initial reactantsused in the practice of the present invention are prepared isadvantageously catalyzed by the presence of an alkali. Useful alkalinecatalysts include soaps, sodium acetate, sodiumhydroxide, sodiummethylate, caustic potash, etc. The amount of alkaline catalyst usuallyis between 0.2% to 2%. The temperature employed may vary from roomtemperature to as high as 200 C. The reaction may be conducted with orwithout pressure, i. e., from zero pressure to approximately 200 or even300 pounds gauge pressure (pounds per square inch).

In a general way, the method employed is subthose mentioned elsewhereherein.

l6 stantially the same procedure asused'for oxyalkylation of otherorganic materials havin reactive phenolic groups.- r

It may be necessary to allowfor the acidity of a resin in determiningthe amount of alkaline catalyst to be added in oxyalkylation. Forinstance, if a nonvolatile strong acid such as sulfuric acid is used tocatalyze the resinification reaction, presumably after being convertedinto a sulfonic acid, it may be necessary and is usually advantageous toadd an amount of alkali equal stoichiometrically to such acidity, andinclude added alkali over and above this mount as the alkaline catalyst.

It is advantageous to conduct the oxyethylation in presence of an inertsolvent such as xylene, cymene, decalin, ethylene glycol diethylether,diethyleneglycol diethylether, or the like, although with many resins,the oxyalkylation proceeds satisfactorily without a solvent. Sincexylene is cheap and may be permitted to be present in the final productused as a demulsifier, it is our preference touse xylene. This isparticularly true in the manufacture of products from low-stage resins,i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated,the pressure readings of course represent total pressure, that is, thecombined pressure due to xylene and also due to ethylene oxide orwhatever other oxyalkylating agent is used. Under such circumstances itmay be necessary at times to use substantial pressures to obtainefiective results, for instance, pressures up to 300 pounds along withcorrespondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such asxylene can be eliminated in either one of two ways: After theintroduction of approximately 2 or 3 moles of ethylene oxide, forexample, per phenolic nucleus, there is a definite drop in the hardnessand melting point of the resin. At this stage, if xylene or a similarsolvent has been added, it can be eliminated by distillation (vacuumdistillation if desired) and the subsequent intermediate, beingcomparatively soft and solvent-free, can be reacted further in the usualmanner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with suchsolvent present and then eliminate the solvent by distillation in thecustomary manner.

Another suitable procedure is to use propylene oxide or butylene oxideas a solvent as well as a reactant in the earlier stages along withethylene oxide, for instance, by dissolving the powdered resin inpropylene oxide, even though oxyalkylation is taking place to a greateror lesser degree. After a solution has been obtained which repre:sentsthe original resin dissolved in propylene oxide or butylene oxide,or a mixture which in eludes the oxyalkylated product, ethylene oxide isadded to react with the liquid mass until hydrophile properties areobtained. Since ethylene oxide is more reactive than propylene oxide orbutylene oxide, the finalproduct may contain some unreacted propyleneoxide or butylene oxide which can be eliminated by volatilization ordistillation in any suitable manner.

Attention isdirected to the fact that the resins herein described mustbe fusible or soluble in an organic solvent. Fusible "resins invariablyare soluble in one or more organic solvents such as It is to beemphasized,- however; that :the: organic: SOIl/entt employed toindicate-r or assure that 1 the? resin.- meets this requirement:needl'not be the. one 'used' in: oxyalkylation. "Indeed solvents:whichi are:

susceptible: to; oxyalkylatiom are :2 included: in this group-oforganic: solvents; Examples of such: solvents" are alcohols:andalcohol-ethers; How?- eyer; where a;resinzisnsoluble'..inran" organic801'?" vent, there are: usually? available other organicsolvents whichare-rnot susceptible to oxyalkyla-- tion,v,useful forthe oxyalkylationstep.- In any; event, the organic-isolvent=soluble resin can-befinely powdered; forinsta-nce; to a 100' to-200 mesh;

andxa slurry or suspension prepared in xylene orthelike; and subjectedtosoxyalkylationr The fact that the resin. is soluble in an organic;solvent or: thewfact 'thatit is fusible, meansthat it consistsofisepara-te molecules-.-; of the type herein'specifiedmossess reactivehy e droxyl groupsand :are oxyalkylation-susceptible.

Phenol-aldehyde resins.

Considerable of --.what-,is said immediately here- Thereason islthat thechloroeoxypropylation may,

vary: the. hydrophile-hydrophobe -balance-in. one; direction .orthe-other, andealsoiinvariably causes. the development .of.. someproperty which makes it inherently different from the ,twoireactants.from which the derivative islobtaineda Referring tothehydroph-ilehydnoxylated intermediates, even moreiremarkable and equally, ditficultto explain, are theversatility and the utility of these compoundsconsidered .as. chemicalireactants as onegoeslfrom minimum hydrophileproperty to ,ultimate maximum hydrophile prop.- erty. For'instance;minimum hydrophile property may be described roughly as the point.where. two ethyleneoxy radicals 0r"moderately in excess thereof areintroduced per phenolic: hydroxyl; Such minimum hydrophile property orsub-surface-activity or minimum surface-activity means that the productshows at least emulsifyingproperties or self-dispersion'in cold'or evenin warm distilled "water (15"to"40 C.) in concentrations 1 of 0.5%to'5.0 Thesematerials are generally more soluble-in'coldi'water thanwarm water, and may even be very" insoluble in boiling" water.Moderately high'temperatures aid in reducing the viscosity of the soluteunder'examination: Some= i alcovezthevindicatedzminiimnn:(2 moles ofethylene oxidewper phenolicmucleusori the equiyalent) but.insufficient-to give za-rsolias described immediatelypreceding,v then,and-a in that event hydrophile prcpertiesare sindicated by; the iactthat one can: I producesanllemulsiomby .havin ;presentt10%: to

18' 501%eof: an inertisolvent such'as xylene. Allthah one'need: tod0ris1to :haveia xylene solution within;the2range;of'.50 to 90 parts'byweight of oxyalkylatediderivatives and:50 to 10 parts by weight ofxylene and mix suchrsolution with-one, two

orzthree timesits-volume 'of' distilled water and shake:vigorously sofasto: obtain an' emulsion& whiclimay'be of the: oil-in-water type or thewaterein-oil type (usually the former) but, in. anyz'eyent; is due tothe hydrophile-hydropho-be balance ofthe oxyalkylatedderivative. Wepre-= fer: simply to use1therxylene diluted derivatives; whichare'described elsewhere, forthis test =rather' thamevaporate :thesolventand employ any more elaborateftests, if;the:solubility isnotsuificientitoi permit the simple sol test in water previously;- noted:

If 1 the product: is: not readily water soluble it may be; dissolved"irr ethyl or: methyl alcohol; ethylene glycol diethyl'et'ner, or"diethylene" glycol diethylether; withitatv little-acetone added' ifre;-= quiredimakingtarather-concentrated solution, for instance*40'.%=to and: then adding enougtr of the concentrated alcoholic or equivalentsolu-ttiorrto give the: previously. suggested 0.5 to'5 .0

, strengh: solution". If' the-product is self-dispers ing-='(i;e:,iifthe oxyalkylatedpro'duct is a -liquid; or a". liquid solutionself=emulsifiable); such $01 or dispersion isvrefrred to" as at leastsemi-stable" in i the SGIISEtIIatISOISJ emulsions; or dispersions:preparedaarezrelatively stable, if they remain at least". forsome-periodiof: time; for instance 39: minutestottwo"hours;before'showing any' marked: separation: Such" tests" areconducted" 'atroom" temperaturei (22"C. Needless to say; a test can bemade-in presence of an insoluble" solvent such as' 5i%=to* 15% ofxylene; as noted in*pre=-- vious examples. Iftsuch'tmixture; ii er,contain; ing-zr azwater-insoluble solvent; is at least" semistable;obviously the solvent 'free product would be: even more :souSurface-activity representing anadvancedrhydrophile hydrophobe balancecan also be determined 'by the use' of conventional measurementshereinafter described. One out standing- "characteristicproperty'indicating' surefa'ce activity in a material is the abilityto'form a permanentfoam in dilute aqueous solution, for example, lessthan" 015%, when in the higher oxyalkylated stage, and to form anemulsion in i thelower'andintermediate stages of oxyalkylation..

Allowance mustbe made for the presenceof" a solventin-the final"product'in relation to the liydrophile properties *ofth'e final product. Theprinciple involved inthemanufacture ofth'e herein contemplatedcompounds" for" use as polyliydfic reactants, is based" on theconversion" of a hydroph'obe or non-hydrophile compound or mixture ofcompounds" into products which are*distinctly liydrophile, at least tothe extent ith'at tliey have emulsifying'proper= ties 'or areself-emulsifying; that is; when shaken with water they produce stableor'semi-stable suspensions, or," in the presence 'of a water=in solublesolvent; such? as" xylene; an emulsion: In :demulsification; itisisometimes preferable to userazprodu-ct having markedlyenhancedhydrophileiproperties overziandfiabove the initial stageof:self="emulsifiability; although we have f-found;thatwithproductszofthetype used herein, most efiicaciouss' results; areobtained i with products which do not lhaverhydrophile properties beyondthe"astage:of:i'selfedispersibility.

Mora-highly; oxyalkylated v resinsi-givexcolloidal solutions: or? sols;which; show typical properties 19' c'bmparable to ordinarysurfacieactive,iagents; Such conventional surface-activity. maybemeasured by determining the surface. tension and the interfacial'tension: against paraffin oil. or" the like. At the initial and'lowerifs'tages' of oxyalkylation; surface-activity. is not i's'uit-=ably determined in this same manner, but one may employ anemulsification .test. Emulsions come into existence as a rule throughthe presence of a surface-active emulsifying agentf Some surface-activeemulsifying agents such as mahogany soap may produce a watereinoilemulsion or an oil-in-water emulsion depending upon the ratio of the twopha es, degree of agitation, concentration of emulsifyingpagent, etc.The same is true in regard to the oxyalkylated resins herein specified,particularly in the lower stage of oxyalkylation, the so-calledsub-sunface-active stage. The surface-activeproper"- ties are readilydemonstrated by producing a xylene-water emulsion. A suitable procedureis asfollows: The oxyalkylated resin is'dissolved in an equal weight ofxylene. 'Such 50-50 solu-- tion is then mixed with 1-3 volumes of waterand shaken to produce an emulsion. The amount of xylene is invariablysufficient to reduce even a tacky resinous product to a'solution whichis readily dispersible. The emulsions so produced are "usuallyxylene-in-water emulsions 1 (oil-inwater'type) particularly when theamount-of distilled water used is at least slightly. in excess of the;volume of xylene Solutiohand also if shaken vigorously. At times,particularlyifin' the:

lowest: stage of oxyalkylation, one'tmay'obtain water in-Xyleneemulsion" '(water in-oil' type-1 which'is apt to reverse" onmoreivigorous' shaking:

and further dilution with water. v If in doubtas to this property,comparison with a resin obtainecl'from para-tertiary butylphenol andformaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using anacidcatalyst and then followed by oxyalkylation using 2 moles ofethylene oxide for each phenolic hydroxyl', is helpful. Such resin priorto oxyalkylation has a molecular Weight indicating about 4 units perresin "molecule. Such resin, when diluted; with an equal weight ofxylene, will serve to illus-.- trate the above emulsification test.

In a few instances. the resinmay not be sufli ciently soluble in xylenealone but may require the addition of some ethylene'glycol diethyletheras described elsewhere. -It' is understood that such mixture, or anyother similar mixture, is considered the equivalent of xylene for thepurposeof this test.

- ;In many cases, there is no doubt as to the presence or absence ofhydrophile or surface-active characteristics in the polyhydric reactantsused in accordance with this invention. Theyqdissolve or disperse .inwater; and such dispersions-foamreadily. With borderline ca es, i. e..'those which show onl incipient hydrophile or surface-active pro e ty(sub-surface-activity) tests for emulsifying properties or self-dispersbility are useful. The fact that a reagent is capable of producing adispersion'in water is proof that it is distinctly hydrophile. Indoubtful cases, comparison can be made with the butyl henol-formaldehyde resin analo wherein 2 moles of ethylene oxide have beenintroduced for each phenolic nucleus.

The presence of Xylene or an equivalent water-' insoluble solvent maymask the point at which a solvent-fr eproduct on mere dilution in a testtube exhibits self-emulsification. For this reason, if it is desirableto determine the approximate point where self-emulsification begins/thenit is better to eliminate the xylene or equivalent from.

a small portion of the reaction mixture and test such port-ion; In some.cases, such' fxylenedree resultant may show initial'or incipienthydrophile.

properties, whereas in presenceof xylene such properties would not benoted. Inqother cases,

the first objective indication of hydropliile proper'ties may be thecapacity of the material to emulsify an insoluble solvent such asxylene. It is to be emphasized that hydrophile properties hereinreferred to are'such as those exhibited by incipient self-emulsificationor the presence of emulsifying properties and go through the range ofhomogeneous dispersibility or admixture with 7,

water even in presence of addedwater-insoluble solvent and minorproportions of common electroregard to the'variation of range ofhydrophil properties, and also in light of-what has been said asto thevariation in theeffectiveness of various alkylene oxides, and mostparticularly of all ethylene oxide, to introduccihydrophile character,it becomes, obvious thatthere is a wide,

variat on; in the amountfof alkylene oxide em:

ployed, as long as it is at least 2 moles per phenolic nu leus, forproducing products useful for the practice of this invention. Anothervariation is the molecular size of'the resin chain resulting fromreaction between the difunctional phenol and the aldehydesuch asformaldehyde. It .is well known that the size. and nature or structureof the .resin polymer. obtained varies somewhat with the conditions. ofreaction, the proportions of reactants, the nature of the catalyst, etc.

- Based on molecular weight determinations, most of the resins preparedas herein described, part cularly in the absence of a secondary heatingstep contain 3 to 6 or '7 phenolic nuclei with approximately 4 /2 or 5nuclei as an average. More .drastic conditions of resinification yieldresins of greater cha n length. Such more inten ive resinification is aconventional procedure and may be employed if de ired. Molecular weight.of courseis measured by any suitable procedure. particularly bycryoscopic methods; but usin t e same reactants and using more drasticconditions of resinification one usually finds that higher molecularweights are indicated by higher melting points of the resins and atendencv to decreased solubility. 'See what has been said else here h rimin r gard to a secondary sep i vol in the heating of a resin with orwithout the use of vacuum.

We have previously pointed out that either an alkaline 'or acid catalystis advantageously used in preparing the resin. Acombination of catalysts is sometimes used in two stages; for instance, an alkalinecatalyst is sometimes employed in a first stage. followed byneutralization and addition of a small amountof acid catalyst in asecond stage. It is generally believed that even in the presence of analkaline catalyst, the number of moles of aldehyde, such asformaldehyde, must be greater than. the moles of phenol employed inanaemic:

21* order rtozrintroducexme hyloli groups in" theointermediate stage.groups appear; in thefinalresin if prepared by the useaofian acidcatalystzv Itiis possible that such groups mayappear in the finishedresins i-prepared solelmwith'an alkaline catalyst; but we have neverbeen .a'blelto, confirm this fact rinaan examination of-i ia? largenumber of resins preparedbyrourselvest Ourpreierence: however, is to use-an-acid-catalyzedwresin, particularly employing a': formaldeahyde-to-phenol ratio of 0.95 to 1.20 and; as faras we-.bave::been ableto determine, such resins are free -from methylol groups. As a matteroffact; it .is' probable that in acid=catalyzed resinificationsa themethylol structure may-= appear only momentarilyrat the'very-beginningofthe reaction and in all probability is convertedat once into a morecomplex structure during the-intermediate stage One procedurewhich canbe employed inthe use of a new resinto' prepare polyhydric reactants tonuse in the preparation of compounds employed in the presentinvention, ioto' determine the hydroxyl value bv the verley-Bolsing methodor--its-'equivalenta The resin as such; or in-th'e formm-fasoluton, asdescribed; is then treat d with ethylene oxide in" presence of 0.5% t 2%of sodium methylate as a a catalyst in step-wise fashion: The--conditions of reaction; as" faras t me "or perc nt are concerned: arewithin the ran e previously--inclicated, With suitable agitation -theethylene oxide; if-added in molecular proportion,- combines withinacomparatively short time. for-instance; a few "minutes to 2 to 6hours;: but in some in tances; requires as much as 8 "to 2 hours; Auseful temperature range is f1f0m*125 tn--225C The completion of the re.action-of "each addition of ethylene oxide in stenwise fashion isusually indicated by the reduction or" e im n t on of-pressure. Anamount conveniently used-foreachj addition is generally eouivalent to-,amole or two moles of ethylene oxide per hydroxvl radical. When theamount ofethylene oxide added 'is eouivalent to approximately 501% by;we ght-"of the original Iresin,,.a,,sample is tested for: incinienthydrophilepmperties by simply shaking upin ater as is. or after theelimination of the solvent if a solventis present The amount of"ethylene oxide used to obta n auseful demulsifying atentlas a .rule.varies from 70% by-weight 0f the original resin to as. much as five orix times theweightof. the original resin. Inzthe'case-of a: resin.derived, .from para-tertiary butylphenol,

as. little .as 50% by ,weightof ethyleneoxide may give, suitablesolubility. With propylene oxide even a greater molecular proportion isrequired and sometimes aresultant oionly-limited hydrophile. properties,is obtainable. Thersameisztrue toeven a greater extentwith butyleneoxide, The;

hydroxylated ralkylene oxides are more eiiective' inasolubilizingproperties 1 tham the comparable compoundsin which no hydroxyl ispresent.

Attention is directed to the -fact that in thesubsequentexamplesrreferenoe isamader to the: step -wise addition of the :alkyleneoxide; such as ethylene oxida It -is understood; of;course, there. is;no objection to" the: continuous addition of alkylon oxide until thedesired stage ofreactionz. is reached, In fact; there maybe less of ahazard; involved, and it is often advantageous :to add the:-

alkylene. oxide. slowly in a continuous stream and in such amount rasstoavoid exceeding the: higher. pressures .noted in the various examplesor. elsewhere! There is no indication-thatrsuch size the fact thatitheseremarkable .oxyalkylated resins. having? surfaceactivity shows unusualpropertieszas: the hydrophile character} varies from a minimum toan-ultimatetmaximum. One should'not underestimate the utility of any: ofthese polyhydric alcohols .in a surface active or" sub-surface-activerange without examiningthem by reaction with epichlorhydrin and subsequently examining the resultant for uti1ity;either-- indemulsificationor in some: other art or: industry, as. referred toelsewhere, oras a reactant for themanufacture of more compli catedderivatives. A few simple laboratory tests: which can be conducted in a:routine manner will usually give all the information that is required.

For instance, a simple: rule to follow iS"tO'pl8- pare aresinhaving atleast threephenolic nuclei and being "organic solventesoluble.Oxyethylate such resin using: the following four ra-tios of moles ofethylene oxide per phenolic unit *equivalent: 2 to 1; 6 to 1; 10 to 1;and 15 to 1. From a sample of each product remove any solvent that maybe present, such as xylene. Prepare 0.5% and 5.0% solutions in distilledwater, as previously indicated; A mere examination of such series willgenerally reveal an approximate range of minimum hydrophile character,moderate hydrophile character, and maximum hydrophile character. If the2-to 1 radio does not show minimunnhydrophile'character by test of thesolvent-free product, then one should test its capacity to form anemulsion when admixed with xylene or other insoluble solvent. If neithertest shows the requiredminimum hydrophileproperty; repetition, using 2%to l moles per phenolic nucleus will serve. Moderate hydro phileoharactershould be shown by eitherthe 6 to 1-or 10 to 1v ratio.Such'moderate hydrophileoharacter is indicated by the fact thatthej. solin distilled water within the previously men tioned'concentration rangeis a permanent trans- 'lucent sol .whenviewedin a comparativelythin:layer, forv instance thedepth of" a test:tube;-. Ultimate hydrophilecharacter is usually shown: at the 1.5to-1:ratiotestLinthataddingrasmall':

.21. amountofan insoluble solvent, for instance =5%;;-

of. xylene; yields .a product which will give; at. least I temporarily;a; transparent or translucent: soli of ithe kind {just described. The"formation of-; a"- permanent foam; .when 1a-0.5% -to 5.0%;aqueouszsolution :is shaken; is an excellent test for :suree face activity:Previous: reference" has been: made to:the fact thatothergoxyalkylatingiagents; may require the use of. increasedamountsxot: alky1ene;oxide: However; it. onerdoes not everi care :to-go;to.:the;tr.ouble :of calculating molecular.-

weightspne. canssimply arbitrarily prepare compounds containinwetliylene oxide equivalent to about-50.%:j.to 75%:.by weight,forexample by. weightgofgthe;resin'to beooxyethylated; as. second;examnle-xusing: approximately: 200% to 300% by weight, and a thirdexample using about 500% to 750% by weight,:. to explore the range.

of hydrophile-hydrophobe' balance.

;A practical examination of the factor of oxyalkylation level can bemade by a very simple test using a pilot plant autoclave having acapacity of about l'to gallons as hereinafter described. Suchlaboratory-prepared routine compounds can then be tested for solubilityand, generally speaking, this is all that is required to,give asuitablevariety covering the hydrophile-hydrophobe range. All these.tests, as stated, are intended to be routine tests-and nothn .:more.JThey are intended to teach'a person, even" though. unskilled inoxyethyla'tion or ojxyalkylation, how to prepare in a perfectlyarbitrary manner, a series'of compounds illustrating thehydrophile-hydrophobe range.

i'lfgone' purchases a thermoplastic or fusible resin on the open marketselected from a suitable number which are available, one might have tomake certain determinations in order to make the'quickest approach tothe appropriate oxy alkylation range. For instance, one should know (a).the molecular size, indicating the number of phenolic units; (1)) thenature of the aldehydic residue, which is usually CH2; and (c) thenature of the substituent, which is usually butyl, amyl, 01' phenyl.With such information one is in substantially'the same position as ifone had personally made the resin prior to oxyethylation.

-For instance, the molecular weight of the internal structural units ofthe resins of the following over-simplified formula:

(n=1 to 13, or even more) is given approximately by the formula: (mol.wt. of phenol -2) plus mol. wt. of methylene or substituted methyleneradical. The molecular weight of the resin would be n times the valuefor the internal limit plus the values for the terminal units. Theleft-hand terminal unit of the above structural formula, it will beseen, is

identical with the recurring internal unit exintroduce, for example, twomolal weights of ethylene oxide or slighty more, per phenolicnucleus..to produce a product of minimal hydrophile character. Furtheroxyalkylation gives enhanced hydrophile character. Although we haveprepared and tested a large number of oxyethylated products of the typedescribed herein, we have found no. instance where the us ofless than 2moles 'ofxethy'leneoxid'e 'per'phenollc nucleus gaver;

desirableproduct's;

' Example 11; throughl'Sb, and the table which appearsin columns51'through 56 of our said state to a sub-resinous or semi-resinous state};.J 4 often characterized bybeing'tacky or stickyyto a final complete'-resin. .As the resin is subjected to oxyalkylation these same physicalchanges tend to take placein reverse. -If one starts with a solid resin,oxyalkylation tends to make'ittacky or semi-resinous and furtheroxyalkylation makes the tackinessdisappear and changes the product to aliquid. Thus, as the resin is oxyalkylated it decreases in viscosity,that is,- becomes more liquid or changes from a solid to a liquid,-particularly when it is converted to .-the water-dispersible orwater-soluble stage. The color of the. oxyalkylated derivative isusually considerably lighter' than the original product from which it ismade, varying from a palestraw color. to an amber or reddish amber. Thevis-- cosity usually varies from that of an oil, like castor oil, tothat of a thick viscoussirup. Some products are waxy.. The presence ofa-solvent,

such as 15% xylene or the like, thins-the viscosity considerably andalso reduces the color in dilution. No undue significance needbe-attached to the color for the reason that if. the same compound isprepared in glass and in iron, the latter usually has somewhat darkercolor. Ifv the resin are prepared as customarilyemployed. in varnishresin manufacture, i. e., a procedure that excludes the presence ofoxygen during the resinification and subsequent cooling of the resin,then of course theinitialresin is much lighter in color. We haveemployed some resins which initially are almost water-white and alsoyield a lighter colored final product. v

Actually, in considering the ratio of alkylene oxide to add, and we havepreviously pointed out that this can be predetermined using laboratorytests, it is our actual'preference, from a prac tical standpoint, tomake tests on a small pilot plant scale. Our reason for so doing is thatwe make one run, and only one, andthat we have a complete series whichshows the progressive effect of introducing 'the oxyalkylatingx agent,for instance, the ethyleneoxy radicals. Our preferred procedure is asfollows: We pre' pare a suitable resin, or for that matter, purchase itin the open market. We employ 8 pounds of resin and 4 pounds of xyleneand place-the resin and xylene in'a suitable auto clave with an openreflux condenser. We pre fer'to heat and stir until the solution iscom-- plete. We have pointed out that soft resins whichare fluid orsemi-fluid can be readily pre'- pared in various ways, such as the useof orthotertiary amylphenol, orthohydroxydiphenyl; V ortho-decylphenol,or by the use of higher mos lecular Weight aldehydes than formaldehyde.-If" producing the chloro-oxypropylatedj Pounds of Ethylene PercentagesOxide Added per 8-pound Batch 66% 5. 33 75 6. O 100 8. 0 150 12. 0 u 200p 16.0 --300 W lt-0 490 32.0 f. 500 140.0 600 -i850 750 60. o

i ixyethylation to 75.0%H6QI1-11S11311Y :becompleted 'mithin .30-=hoursandfrequently more quickly.

Elie-{samplestaken-are rather small, for instancmzz toieounces so thatn0 correction need be made in regard to theresidual-reaotion mass.liachz zsampleeis ,divided. ingtwo. ,One half the asample is .iplaeeddnean' evaporating dish -.on:the asteam pathxj-oyernight so "as-toeliminate' the xylene. Then. 1-.5-%::solutions are-prepared from "both'series'.oflsamplEs,ripe; the series with xylene ipresentland the=1S8IiflS with xylene? removed.

:Mere wisual examination of 3 any samples in .zsolutionmayebeasumcientcto indicate hydrophile @eharacter. or -surfaceqa'ctivity i.v e.,w theproduct is soluble, donning a =colloidal1-so1, orthe @aqueous solution ;-:fo ams 15 .01 -,shows.,=emulsifyin +property.

these propertiesrlare related. through" adsorpanibemeasured inanyqne ofthe; usual ways; Sing: :a 'DuNouyptensiometer or zdropping pipette,-or,:anyy-other .procedurerfor measuring interfacial.tension. :Suchtests {are eenvention-al and requirei no further description. M ycompound having subzsurface -activity,= and all derived=from the sameresin, and oxyalkylated ato a greater extent,=i: e., thosehaving agreater .l proportion of alkylene oxide, are,- usefulas, poly- -hydricreactants -10! ,-the ge-practice, of ;-thisyinvvention.

:Anotherreason :Why we, prefer to, use a pilot 26 froma mixtureof;phenols havinglpresent 1%-:or -;2% a of a triiunctional zphenol:which willresult in. an insoluble rubber at the ultimate stages-ofoxyethylation but not in theearlier stages. din

5 -other words, with'resinsfronnsome'such phenols,

plant -testtoi the-k-ind above described is that extensiveoxyethylation. lt is also obvious that one may have a solvent-solubleresin derived :addition of 2 or 3 moles eof -theoxyalkylating agent perphenolic nucleus, particularly ethy-lene oxide, gives a suriace activereactant which .perLectly satisf-actory, whilemore extensive oxy--ethylation yieldsan insoluble rubber, that is,- a-n unsuitablereactant.-It--is obvious that-this presentprocedure lof eva'luating-;trifuncti'onal. phenol tolerance is more suitable than the previousprocedure.

It may be well to call attention to one result which may be noted in along drawn-out oxyalkylation, particularly oxyethylation, which wouldnot. appear in a normally conducted reaction. {Reierence has been madeto cross-linking and'its effect on solubility and alsothe fact that,ifgcarried'far enough,'it causes incipient stringiness, then pronouncedstringiness, usually foLowed by a semi-rubbery or rubbery stage.Incipient stringiness, or even pronounced stringiness, or eventhetendency toward a rubbery stage, is'hot objectionable sofjlong as the"filial "I'JrOuuct 'is still hydrophile, and at least subsurface-active.Such material frequently is best mixed with a polar solvent, suchasalcohol or theilike, and prefra'blyan alcoholic solution is 'used. Thepoint'which we want to' make here, "'liowever, "is this Stringinessorrubberiz'ationat 'thisstage' may p'ossiblylbe', the result of'etheri'fication. Obviously if 'a' 'difunctional phenol and an aldehydeproduceja 'noncr'o'ss-linked resin 'molecule and ifsuchjmolecule is'oxy'alkylated so asto intr'o'du'cefa plurality of hydroxyl groupsiin'e'achm'olecule, then an'd'in'th'at event'if subsequent 'etherificati'ontakes'iplacej one is going [to obtain cross-:linkin'ginjthes'ameg'eheral way that one WOlIl'd obtain cross-linking in otherresinification reactions. Ordinarilythere is'little or'fno tendencytoward ethefi'i'fication during the oxyalkylation step. Ifjitfdoestakeplace at alljit is onlyto an insignificant "and undetectable'jdegree.Howevenf'suppose that 'a'cer'tain 'weight'of resin is treated withi'anequal weight of, or twice its weight "of, ethylene, oxide. Thisn'iay bedone in fa comparatiyely short'time, for instance, "at crave c. in4"to 8"hour's,for even less. on the other hand, if in "an exploratoryreaction, such'as the kindpreviously described,'the ethylene oxide wereaddedextremely slowly inorder to take stepwise samples, so that thereaction required 4 or'5 times as long to introduce an equal amount ofethylene oxide employing ,the same temperature, then etherificationmight cause stringiness or a suggestion of rubberiness. For this reasonif in. an exploratory experiment of the kind. previouslydescribedthere-appears to be any stringihess or"rubloer-iness,. itiniaybewell to repeat the experiment and reach the intermediate stage ofoxyalkylation as rapidly as; possible and then proceedslowly-beyondthisintermediate stage. 'The. entire purpose of this modified procedure isto cut down --the time of're action so as'to avoid etherification if itbe caused by the extended time period.

It may be well to; n0te one-peculiar reaction sometimes, noted in the-course1of oxyalkylation, particularly oxyethylation, of thethermoplastic resins-herein described. Thisrefiect is note'din' 'a caseWhere a thermoplastic .resin has i been: oxyalkylated, for (instance,,oxyethy1ated, until :it gives a perfectly clear solution, even in thepresnce of some accompanying water-insoluble solvent such as to ofxylene.-' Further oxyalkylation, particularly oxyethylation; 'may thenyield a product which, instead of giving-a clear solution as previously,gives avery milky s01uti0n suggestingthat some-marked changehas takenplace. One explanation of the above --'change is that the structuralunitindicated in the following way where 8n isa fairly large number, forinstance, 10 to-20, decomposes and-an '"oxyalkylated resin representinga lower degreeof oxyethylation and a less soluble one, isgenerateda'ndacyclic polymer of ethylene oxideis produced, indicated thus: I

28 should be non-reactive to the alkylene oxide'eniployed. Thislimitation does not apply to solvents used in cryoscopic determinationsfor obvious reasons. Attentionis directed to thefact that variousorganic solventsmay be employed to verify that the resin is organicsolvent-soluble. Such solubility test merely characterizesv the resin.The particular solvent used in such test may not be suitablefor amolecular weight determination and, likewise, the solvent used indetermining molecular weight may not be suitable as a solvent duringoxyalkylation. For solu tion of the oxyalkylated compounds, or theirThis fact, of course, presents no difficulty forlthe reason thatoxyalkylation can be conduc'tedin each instancestepwise, or" at agradual rate, and samples taken at short intervalsso as to arrive at apoint where optimum surface activity or hydrophile character is obtainedif desired; for products for use as polyhydric reactants in. thepractice of this invention, this is not necessary land, in fact, maybeundesirable, i. e., reduce the efficiency of the product.

We do not know to what extent oxyalkylation produces uniformdistribution in regard 'tophe- 'nolic hydroxyls present in theresinmolecule. In

some instances, of course, such distribution canj not be uniform for thereason thatfwe'ha'venot 40 specified that the molecules "of ethyleneoxide, for example, be added in multiples of the unit's present in theresin molecule. This'may be illustrated in the following manner: iSuppose the resin happens to have fivephenolic .nuclei. If a minimum'oftwo moles, of ethylene jjoxide per phenolic nucleus are added, thiswould jmean an addition of 10 moles of ethylene oxide, i b'ut supposethat one added 11 moles of ethylene ,oxide,'or 12, or 13, or 14 moles;obviously, even assuming the most uniform distribution possible, "someof the polyethyleneoxy radicals would contain 3 ethyleneoxy units andsome would contain 2.. Therefore, it is impossible to specify uniform:distribution in regard to the entrance of the eth- ".ylene oxide orother oxyalkylating agent. For 'that matter, if one were to introduce 25moles of ethylene oxide there is no way to be certain that an chains ofethyleneoxy units would have 5 "units; there might be some having,forexample, 4.- and 6 units, or for that matter 3 or '7 units. *N or isthere any basis for assuming that the number of molecules of theoxyalkylating agent added to each of the molecules of the resin is thesame, or'difierent. Thus, where formulae are given to illustrate ordepict the oxyalkylated products, distributions of radicals indicatedare to be statistically taken. We have, however, included specificdirections and specifications in regard to the total amount of ethyleneoxide, or total amount of any other oxyalkylating agent, to add. Inregard to solubility of the resins and the :oxyalkylated compounds, andfor that 'matter derivatives of the latter, the following should be:noted. In oxyalkylation, any solvent employed employed, such asalcohols, ether alcohols, cresols, phenols, ketones, esters, etc., aloneor with the addition of water. Some of these are mentioned hereafter.-We prefer the use of benzene or diphenylamine' as a'solvent in'makingcryoscopic measurements. The most satisfactory resins are those whichare soluble in xylene or the like, rather than those which are solubleonly in some other solvent containing elements other than carbon andhydrogen, for instance, oxygen or chlorine. Such solvents areusuallypolar, semi-polar,.or slightly polar in nature compared withxylene, cymene, etc. s

Reference to cryoscopic measurement is concerned with theuseof benzeneor other suitable compoundas a solvent. Such method will show thatconventional resins obtained, for example, from para-tertiary amylphenoland formaldehyde, in presence of an acid catalyst, will have .amolecular weight indicating. '3, l, 5: or somewhat greater number ofstructural units per molecule. If more drastic conditions ofresinification-are employed, or'if such low-stage resinissubjected --toavacuum distillation. treatment as previously described, one obtains aresin of a. distinctly higher molecular weight. Any-molecular weightdetermination used, whether cryoscopic measurement or otherwise, otherthan the conventional cryoscopic one employing benzene, shouldbecheckedso as to insure that it gives consistent values on suchconventional resins as a control. Frequently all that is necessary tomake an approximation of the'molecular weight range is to make aeomparison With-the-dimer obtained by chemical combination of twomoles-of the same phenol, andonemole of the same aldehyde underconditions to insure dimerization; 'As to} the preparation of suchdimers from substituted phenols, see Carswell Phenop1'asts,- page 31.The increased viscosity, resinous character, and decreased solubility,etc; of 'thehigher polymers, in comparison with the dimer, frequentlyare all that is required to establish that the resin contains 3 or morestructural units per molecule.

Ordinarily, the oxyalkylation iscarried out in autoclaves provided with"agitators or stirring devices. We have found that the speed of-theagitation markedly infiuencesthe-reaction time. Insome cases, the changefrom slow speed agitaltionrfor exam lefin a laboratory autoclave agice." l o. v-. -lv

derivatives a great variety of solvents may be tation with a stirrerocrating atarspeed of 60 to 200 R. P. M., to high speed agitation, withthe stirrer operating at 250 to 350 R. P. M., reduces the time required;for. oxyalkylation by about one-half to two -thirds. Frequently I xylene-soluble products which give insoluble. products by procedures employingcomparatively. slow speed agitation, ive suitable hydrophileproducts,when produced by similar procedure, but with high speed agitation, as aresult, we believe, of the reduction in the time required, withconsequent eliminationor curtailment of opportunity for curing or;etherization. Even if the formation of an insoluble product is notinvolved, it is frequently advantageousto speed up the reaction, therebyreducing production time, by increasing agitating speed. In large scaleoperations, we have demonstrated that economical manufacturing resultsfrom continuous oxyalkylation, i.'"e., an operation in which-thealkylene oxide is continuously fed to the reaction vessel, with highspeed agitation, i. e., an agitator operating at 250to 350 R P. M.Continuous oxyalkylation, other conditions being the same, is more rapidthan batch oxyalkylation, but the latter is ordinarily moreconvenientfor laboratoryoperation.

Previous reference has beenmade to the fact that in preparing compoundsof the kind herein described, particularly adapted for demulsificationof water-ineoil emulsions, and for that matter, for other purposes, oneshould make a com- -.plete exploration-of the wide variation inhydro-.phobe-hydrophile balance, .as previously referred to. It has beenstated, furthermore, that this hydrophobe-hydrophile balance of theoxyalkylated resins is impar-ted,as:far as thesrangetof variation goes,to a greater or lesser extent to the hereindescribed derivatives. This:means that one employing the present invention should take the choiceof the most suitablederivative selected froma number of representativecompounds, thus, not only should a variety of resins be preparedexhibiting a variety of oxyalkylations, particularly oxyethylation, butalso a variety of derivatives. This can be done conveniently "ifilight"of what has been said" previously. From a practical standpoint, usinpilot plant equipment, for instance, an autoclave, having a capacity ofapproximately three to five gallons. We have made a single run byappropriate selections in which'the molal ratio of resin equivalent toethylene oxide is one to one, 11to 5, 1 to 10, 1 to 15, and 1 to 20.Furthermore, in making these particular runs we have used continuousaddition of ethylene oxide. of ethylene oxide we have employed eitheracylinder of ethylene oxide without ia'dded nitrogen, provided that thepressure of the ethylene oxide was sufficiently great to pass into theautoclave, or else we have used an arrangement which, in essence, wasthe equivalent of an ethylene oxide cylinder with a means for injectingnitrogen so as to force out-the ethylene oxide in the manner ofanordinary. seltzer bottle, combined with the means for either weighingthe cylinder .or measuringthe ethylene oxide used volumetrically. .LSuchprocedure and arrangement for injecting liquids is, of course,conventional. The following data sheets exemplify such operations, 1.e., the combination of both continuous agitation and taking samples soas to gi five d fieren variants in oxyethylation. In adding ethyleneoxide continuously, there is one precaution which must be taken at alltimes. The addition of ethylene oxide must stop immediately if there Inthe continuous addition .is any indication that reaction is stopped, or,

obviously, if required is not started at the beginning of the reactionperiod. Since the addition of ethylene oxide is invariably an exothermic"reaction, whether or-not reaction has takenplace can be judged in theusual manner by observing (a) temperature rise or drop, if any, (b)amount of cooling water or other means required to dissipate heat ofreaction; thus, if there is a temperature dropwithout the use of coolingwater or equivalent, or if there is no rise in temperature without usingcooling water control, careful investigation should be made.

In the tables immediately following, we 'are showingthe maximumtemperature which is usually the operating temperature. In other words,by experience we have found that if the initialireactants are raised tothe indicated tern,- perature and then if "ethylene "oxide is 'addedslowly, this temperature is maintained by cooling water until theoxyethylation is complete. We have also indicated the maximum pressurethat we obtained or the pressure range. Likewise, we have indicated thetime required to inject the ethylene oxide as well as a brief note as tothe solubility of the product at the end of the oxyethylation period. Asone period ends it will .be noted we have removed part of theoxyethylated mass to give us derivatives, as therein described; the resthas been subjected to further treatment. All this 'is apparent byexamining the columns headed Starting mix, Mix. at .end .of. reaction,Mix which is removed forsamplefand Mix which remains as next starter.

The resins employed are prepared in the manner described in ExamplesNos. 1a through 10311 of our said Patent 2,499,370, except that insteadof being prepared on a laboratory scale they were prepared in 10 tol-5-gallon electro-vapor heated synthetic resin pilot plant reactors, as

manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, andcompletely described in their Bulletin No. 2087, issued in 1947, withspecific reference to Specification No. 71-3965,

For convenience, the following tables give the numbers of the examplesof our saidPateti't 2,449,370 in which the preparation of identicalresins'on laboratory scale are described. .It is understood that in thefollowingzexamples, the change is one with respect to the size of theoperation.

The solvent used in each instance was xylene. This solvent isparticularly satisfactory for "the reason that it can be removed readilyby distillation or vacuum distillation. In these continuous experimentsthe speed of the stirrer in the'autoclave was 250R. P. M.

In examinin the subsequent tables it will be noted that if acomparatively small sample is taken at each stage, for instance,one-half to "one gallon, one can proceed through the entire molal stageof 1 to 1, to 1 to 20, without remaking at any intermeditae stage. Thisis illustrated by Example 104a. In other examples 'wefourid it desirableto take a larger sample, for instance, a B-gallon sample, at anintermediate stage. As a result it was necessary in such instances tostart with a new resin sample in order to prepare sufficientoxyethylated derivatives illustrating the latter stages. Under suchcircumstances, of course, the earlier stages which had been previouslyprepared were bypassed or ignored. This is illustrated in the tables,where, obviously, it shows that the starting mix was not removed from aprevious sample.

Phenol for resin: Para-tertiary amy lphenol Aldehyde for resin:Formaldehyde gb st uw b 22,1948 'l Q 7 [Resin made in pilot plant sizebatch, approximately 25 pounds, corresponding to 3a of Patent 2,499,370but this batch designated 1040.]

- Mix Which is Mix Which Restarting Mix fig figg of Removed for mains asNext Sample Starter MBA. Max. Time 1tljressure '{emp ergahrs SolubilityLbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

Lbs Lbs. Lbs Lbs Sol- Res: Sol- Res- 801- Res- Sol- Res-. vent in Etovent, in Eto vent in vent in Eto First Stage .iBesin to M0. V

M0121 Ratio 1: 1. 14. 15. 75 0 14. 25 15. 75 4. 0 3. 3.65 1. 0 10. 9 12.1 3. 0 80 150 M I =Ex. No.'104b....- I V V Second Stage i .Resin t'oEtO... .Molal Ratio 1:5- 10 9 12.1 3. 0 10.9 12.1 15. 25 .3. 77 4. 17 5.31 7. 13 7. 93 9. 94 158 la ST -E-x. Nb. 1051)... 1

IThird Stage Resin to EtO--.. V Molal Ratio 1:10. 7 13 7. 93 9. 94 7. 137. 93 19. 69 3. 29 3. 68 9. 04 3. 84 4. 25 10. 65 60 173 $5 FS Ex. N o.10Gb. 0 Fourth Stage Resin to EtO....

Molal Ratio 1:15. 3 84 4.25 10.65 3.84 4.25 16.15 2. 04 2.21 8.55 1.802.04 7.60 '220 160 16 RS Ex.No.107b- I Fifth Stage Resin to EtO MolalRatio 1:20. 1 2.04 7.60 1.80 2.04 10L2 $6 QS Ex. No. 10821.

1 In soluble. ST Slight tendency toward becom ing soluble. FS Fairlysoluble. RS Readily soluble. Q S Quite soluble.

. Phenol for resin: Nonylphe'nol Aldehyde for resin: Formaldehyde Date,June 18, 1948 [Resin made in pilot plant size batch, approximately 25pounds, corresponding to 70a of Patent 2,499,370 but this batchdesignated 109a.]

Mix Which is Mix Which Re- Starting Mix fig ggg of Removed for mains asNext Sample 7 Starter Max. Max. Time R1, IBSSll10 'gemp eri- SolubilityLbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. we, I

. Lbs. Lbs. Lbs. Lbs. Sol- Res- Sol- Res 801- Res- 801- Resvent in Etovent in Eto vent in Eto vent in Eto First Stage ;';Res1n to EtO.... IM0lal Ratio 1:1. 15 0 l5. 0 0 15. 0 15. 0 3 5. 0 5. 0 1. 0 10. 0 10. 02. 0 50 150 1% ST 'Ex. N0. 109b.-... I Second Stage ,Resint0EtO.... y MMolal Ratio, 1:5. 10 1O 2. 0 10 10 9. 4 2. 72 2. 72 2. 56 7. 27 7. 27 6.86 100 147 2 DT hx.No.110b.... 0 Third Stage I .Resin t0 Et0 W MolalRatio 1:10. 7 27 7. 27 6. 86 7. 27 7. 27 13. 7 4. 16 4. 16 7. 68 3.15 3.15 5. 95 125 1 S E .N0.111b...-- k Fourth Stage .Resin to EtO... MolalRatio 1:15. 3. 15 3.15 5. 95 3. 15 3. 15 8. 95 1. 05 1. 05 2. 95 2. 102. 10 6. 00 220 174 2% S Ex. No. 1125.....

mm Stage Resin to Et0. Molal Ratio 1:20. 2. 10 2. 10 6. 00 2. 10 2. 108. 00 220 183 3:; VS Ex. No. 113b...

"" S=Soluble. ST=S1ight tendency toward solubility. DT=Definite tendencytoward solubility. VS=Very soluble.

I Phenol for. resin: Para-oetylphenol v I Aldehydeforresin: FormaidehydeDate, June 23, 24, 1948 [Resin made in pilot plant sizebatch;approximately 25 pounds, corresponding to 812 of Patent 2,499,370 butthis batch designated 1145.]

-Mix Which is Mix Which Re- Starting Mix g fig of Remover] for mains asNext Sample Starter M 9.1. Max. Time 4 Pressuge Tempgm- Solubility lbls.gm. Lbs i b s. I bs. Lbs I b s. 1... Lbs x b s. abs. Lbs

oesoes- 0- es- 0- esvent in Eto vent in Em vent in Eto vent in Eto FirstStage Resin to EtO..-. Molal Ratio 1:1 14. 2 15.8 0 14. 2 15.8 3. 3. 13.4 0. 75 11. 1 12.4 2. 5 150 1%: NS '15:. No. 1145.-- W

Second Stage Resin to EtO-... M0181 Ratio 125.- 11.1 12.4 2.5 11.1. 12.412.5 7.0 7.82 7.88 4. 1 4. 58 4.62 100 171 M 88 Ex. No. 115b....

Third Stage Resin to EtO-. MolaLRatio 1:10- 6.64 7.36 "0 6.64 7. 36 15.0120 190 1% S Ex. No. 1165--- Fourth ,Stane Resin to Et0-.-. Molal'Ratio1:15. 4.40 4.9 Z0 4.4 4.9 14.8 400 160 M VS Ex. No. 1175.....

Fifth Stage Resin to Et0-..- M0181 Ratio 1:20. 4. 1 4. 58 4. 62 4. 1 4.58 18. 52 260 172 k; VS ExJ'No. 1185...

S Soluble. NS- Not soluble. SS= Somewl 1 at soluble. VS=Very soluble.

Phenol for resin: Menthylphenol' Aldehyde for resin: Formaldehyde new,July 8-13, 1948 [Resin made in pilot plant size batch, approximately 25pounds, corresponding to 69a of Patent 2,499,370 but this batchdesignated 11911.]

' Mix Which is Mix Which Re- Starting Mix figg ggg of Removed for mainsas Next Sample Starter Max. Max. Time Pressure Tempgmhrs Solubility'gbls. Ibs. Lbs Lbs. 115. Lbs 1 1, 5. Ifibs. Lbs gbis. abs. Lbs ture oeses- .0 eso esvent in Eto vent in Eto vent in Eto vent in First Stage 1Resin to Et0-.-. i .Molal Ratio 13.65 16.35 ,0 13.65 16.35 6.0 9. 11.45'2.1- 54.1 4.9 0.9 150 1% NS Ex. No. 1195.- I a j 5 Second Stage I LRinto m1-.. 4 i g 2 5 olal Ratio 1:5-- 10 12 0 10 1 12 10. 4. 52 5.42 4.81 5. 48 6. 58 5. 94 140 V 160 1%: 8 Ex. No. 120b.....

Third Stage Resin to momi 1 Molal Ratio 1:10- 6. 48 6.58 v 5. 94 5.486.58 10. 1 l M 8 Ex. No. 1210""- I 5 I r I Fourth Stage 5 g Resin tomom. 1 i l Molal Ratio 1:15- 4.1 4.9; 0.9 4.31 4.9 13.15 180 171 1%: VSEx. No. 1220... g g g Fifth sed e i Resin to EtO..-. l M0121 Ratio 1:20-v3.10 3.72 0.68 3. 210 3. .72 13.43 320 54 VS EX. NO- 123b i l r iB-Solubln. INS-Not Soluble. VB-Very soluble.

Phenol fb'r 755m: Pard-secoitdarg butylphmbt Date, July 14-15, 1948A'tdehyd far resin." Formaldehyde R'sirk made 1x11311015 plant sizebatch, apprdximteij' 25 pounds,;eorresponding 55125 of mtwmgzamsmbutthis 155555 designated 1245.]

Mix at End oi Sample Mix which Removed for Sol- Resvent in Eto vent: 1n

Lbs. Lbs. L155. Lbs.

Sol- 'Rps "801' 511125 vent EtO Max.

Time,

First Stage [Rsinmade on pilot piafit'size batch, approximately p'ounds,corresponding to 8100! Patent 2.499.370 bu't'thisbatch designated 129a,]

Third Stage Resin ,to EtO Molal Ratio 1:10- 4.52 5.18 o 4.52 515114.2540oxss 3 Ex. No. 1255 Fourth Stage Besin toEtonh. I 3 V Molal Ratio1:15- 5.55 4.15 o 3.55 4.15 17.0 220 150. 35 vs Ex.No.127b

Fifth Stag'e ResintoEtOw v I 3 Molal Ratio 1:20.}2. 65 2.85 4.95 2. 552.85 15.45 so 511 V8 Ex. No. 1281) s =Solub1e. NS=Not soluble. ss=son15wha5's'otub1e. vs= Very 15111515.

1 Phehatfor rbstn: M555 1 Aldehyde for resim Pf'bpiandldehydt DateAugust 12-13, 1948 Mix at; End of Startin Mix Reaction Mix Whleh '13Removed for Sample vent vent Max.

Tempera- T if f Solubility First Stage Resin to EtQ Mela! Ratio 1 Ex.No. 129!) Second Stage Resin to E50...

M01111 Ratio 1 Ex. NO. 13011....

Third Sta'ge Resin to 13150 Molal Ratio 1:10 Ex. No. 13112..--"

Fourth Stage Resin to Et( Molal Ratio 1: 16- Ex. No. 13211 Fifth StageResin to EtO M0151 Ratio Ex. No. 1330..----

150 Nq t soIubla.

170 Somewhat soluble.

54; Soluble;

'54 Vgr'y solub le.

Date, Angnst 2741,1948 V Phenol for resin: Para te'm'ary amylphenolAldehyde for resin: Furfural size batch, approximately 25 pounds,corresponding to 42a of Patent 2,499,370 but this batch designated as154a.)

' [Resin made on pilot plant Mix Which is Mix Which Re- Starting Mix gfigg of Removed for mains as N ext Sample Starter Max. Max. TimePressure Temgerahrs Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.ture S01- Res- Sol- Ros- Soi- Res- Sol- Resvent in vent in vent. in tvent in t First Stage Resin to EtO Molal Ratlo 1:1 11- 2 18. 0 11. 2 18.0 3. 5 2. 75 4. 4 0. 85 8. 13. 6 2. 65 120 135 56 N01; soluble. Ex. No.1346---.-. V

Second Stage Resin to Et0- Molal Ratio 1'5 3. 45 13. 6 2. 65 8. 45 13. 612. 65 5. 03 8. 12 7. 3. 42 5. 48 5. 10 110 150 ,4 Somewhat -E::. No.13511 s soluble.

Third Stage Resin to Eton--- M01al Ratio 1:10 4.5 8. 0 4. 5 8.0 14. 5 2.45 4. 35 7.99 2.05 3. 6. 60 180 163 $4 Soluble.

EX. N0. 1360 Fourth Stage Resin to EtO -Moia1 Ratio 1:15-. 3.42 5.48 5.10 3.42 5.48 '15. 10 180 188 }6 Very soluble.

Ex. No. 1376------ Fifth Stage Resin to EtO. -Molai Ratio1:20 2.05 3.656.60 2.05 3.65 13.35 120 125 is Verysoiuble. Ex. No. 13812 Date, Sept.23-24, 1948 [Resin made on pilot size batch, approximately 25 pounds,corresponding to 89a of Patent 2,499 370 but this batch designated as13%.]

Phenol-forresin: Menthyl Aldehyde for resin: Furfural' Mix Which is MixWhich Re- Starting Mix fig ggg of Removed for mains as Next SampleStarter Max. Max. Time Pressure Temp era- Solubility Lbs. Lbs. Lbs. Lbs.Lbs. Lbs. Lbs. Lbs. C 801- Res- Sol- Res- Sol- Res- S Resvents in ventin vent in vent in 4 First Stage Resin to EtO- Molal Ratio 1:1--- 10.2517.75 10.25 17.75 2.5 2.65 4.60 0.65 7.6 13.15 1.85 90 150 Not Soluble.Ex. No. 13954.."

Second Stage Resinto EtO ..-Molal Ratio 1:5..- 7.6 13.15 1.85 7.6 13.159.35 5.2 9.00 6.40 2.4 4.15 2.95 177 $6 SOmeWhat Ex. No. 140b.---.- ssoluble.

Third Stage Resin to EtO- MolaiRati01:10 4.22 6. 98 4.22 6. 98 10.0 1654'2 Soluble. Ex.N0.141b

Founth Stage Resin to EtO- .Molal Ratio 1;15 3.76 6.24 3.76 6.24 13. 100171 $4 Verysolubie. '-Ex.No.142b I Fifth Stage Resin to EtO.....Mola1Ratio1:20- 4.15 2.95 2.4 4.15 11.70 90 Ma Verysolnble. Ex. No.l43b- I Date, October 7-8, 1948 Phenol for resinxParawctyl [Resinmade onpilot plant size batch, approximately pounds, corresponding to 42a ofPatent 2,499,370 with 206 parts by weight of commercial para-octylphenolreplacing .164 parts by weight of para tertiary-amylphenol'butthxs batchdes1gnatedaas144m] Mix Which is Mix Which Re- Starting Mix gg of Removed'for mains asNext Sample Starter Max Pressure 'Tempera- Time Solubilitylbs sr in 'ture "0 Lbs. Lbs. Lbs. .Lbs. Lbs. .Lbs. Lbs. .Lbs. Sol- Res-83 Sol- Ites- 138 Sol- R- ga "801- Res- 23 vent in vent in went in ventin First Stage Resin to 'Et0.... Molall Ratio 1:]... 12.1 18. 6 12. 118. 6 3.0: 5.38 8. 28 1.34 6. 72 10.32 1. 66 .80 150 M2 ID5011111113.-Ex. No. 1446...--- i Second Stage Slight tend- Resin to EtO.... .ency1:0- MolalRatio 1.25.. 9-. 25 14. 25 9. 25 .14. 25 11. 0 3. 73 '5. 73 4.44 *5. 52 8. 52 '6. 56 100 177 iz be- Ex. 'Nn.145b.-. commgsoluble.Third Stage Resin to Et0.... Molal'Ratio 1;:10. -6.'72 10. 32 1. 66 6.72 1'0. 32 14. 91 4. 97- 7. 62 11. 01 1. 75 2. 70 '3. 90 182 $4 Fairly.solu- Ex. No. 1466.--" 'ble.

Fourth Stage Resin to E.tO -Mo1e1 Ratio 1:15. 5. 52 8.52 6. 56 5. 528.52 19.81 100 176 -16 Readily 501- Ex. No. 1476.... uble.

F1fth Stage Resin to E10. M0121 Ratio 1:20- 1. 75 2. 70 3. 1. 75 2. 708.4 80 160 34 Quite .50111- Ex. No. 1486. ble.

Date, October 11-13, 1948 Res'in'made on pilot plant size batch, a

Phenol for 'res'i'm Pam-phmyl Alde'hyde forresin: Furfuml pproximately25 pounds, corresponding-to 42a of Patent 2.499.370 with 170 partsby-weight of commercial paraphenylphenol replacing 164 parts by weightof para-tertiary amylphenol but this batch designated as 14911.]

. Mix Whicnis Mix W'hichRe Y Starting Mix gig f figg Removed for mainsas Next Sample Starter Max. Max. Time Pressure Temp erahm Solubilitylbls. libs. Lbs Ibls. .Ifibs. Lbs gbls. fins; Lbs .r b s. fl r bs. Lbs

0- es- 0- es-. oes-- ',.o- 195- vent in Eto vent in Eto vent in Eto ventin Eto First Stage :Resinto E600 Molal Ratio 1:1-- 13. 9 16. 7 13.9 16.7 3.0 3. 50 4. 25 0. 80 10.35 12. 45 2. 20 Insoluble. Ex. No. 149b.-.

Second Stage Resin'to' 310.. l hg mi Molal Ratio 1=5.. 10.35 12. 45 2.2010.35 12. 45 12. 20 5.15 s. 19 6.06 5. 20 6.26 6.14 so 183 g5 3 9' Ex.No. 1501:--." P?

bihty.

Third Stage Resinto 'EtO.-. i Mblal Ratio 1:10. 8.90 10.7 8. 90 10.7019.0 5.30 6.38 11.32 3.60 4.32 7.68 90 193 1A2 Fairly 5011.1. Ex. No.151b-,.--. ble.

Foimh Stage -Resin to 13110.--. Molal Ratio 1:15. '5. 20 6.26 6.14 5. 206. 26 16.64 100 171 1'6 .Readfly $01- Ex. No. 152b-.-. uble.

Fifth Stage Resinto EtO-. 1 Molal Ratio 1:20. '3. 60 4. 32 7. 68 3. 604. 32 15. 68 Sample somewhat rubbery and gelat- 230 2 Ex. N0. 153b--inous but fairly soluble

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE,CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING A CHLORO-OXYPROPYLATED DERIVATIVE OF HYDROPHILE HYDROXYLATEDSYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEINGOXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOTMORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OFETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE, ANDMETHYLGLYCIDE; (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANICSOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOLALDEHYDE RESIN; SAID RESIN BEINGDERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND ANALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL;SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONALPHENOLS; SAID PHENOL BEING OF THE FORMULA: